This invention relates to silicon based quaternary ammonium functional compositions and to methods for making such compositions. More particularly, the invention relates to certain novel quaternary ammonium functional silicones and silanes, as well as methods to make quaternary ammonium functional silicones and silanes using cationizing agents.
Quaternary ammonium functional organic materials are well known in the art. They can be made by methods such as the exhaustive alkylation of amines by alkyl halides. Because of their positive charge. quaternary ammonium functional organics are useful in treating materials/surfaces that are primarily negatively charged, such as in many textile and personal care applications. These materials have also been found to exhibit anti-microbial activity.
It has been found that cationic modification of polymers (including those making up fillers, fibers and surfaces, organic or silicon based) through addition or formation of quaternary ammonium functionality makes possible certain ionic interactions that are the basis of many useful properties (or their enhancement) and thus applications of such modified materials. These include increase in hydrophilic character, ability to act as a thickener and improved ability to pickup other materials such as dyes, coatings and conditioning agents.
Recently, such modification has been described for starch in PCT publication WO 99/62957 and for chitosan in the article by Loubaki et al. in 27 Eur. Polym. J. 3:311-317 (1991). In the former, the cationizing agents, 2,3-epoxypropyltrimethylammonium chloride or equivalent chlorohydrin functional materials were used. Glycidyl trimethylammonium chloride was used in the work reported in the latter reference with reaction taking place at the amino groups of the chitosan.
Quaternary ammonium functional silicones and methods for making them have been known in the art for a number of years. For example, Reid in U.S. Pat. No. 3,389,160 discloses a group of these materials and a two step method for making them. In the first step, an epoxy functional silicone is reacted with a secondary amine to form a tertiary amine functional silicone. The product is reacted with an alkyl halide to yield a quaternary ammonium functional silicone in the second step.
Margida in U.S. Pat. No. 4,895,964 discloses certain pendant quaternary ammonium functional silicones and a one step method for making them. Here, a tertiary amine salt is reacted with a pendant epoxy functional silicone. A group of terminal quaternary ammonium functional silicones is disclosed by Schaefer et al. in U.S. Pat. No. 4,891,166, as well as a method for making them, which is similar to the method in Margida, except that a terminal epoxy functional silicone is used.
McCarthy et al. in U.S. Pat. No. 5,164,522 discloses a class of quaternary ammonium functional silicones and a method for making them; the method involves treating diamine functional silicones with ethylene oxide followed by reaction with dimethyl sulfate. In U.S. Pat. No. 5,098,979 to O""Lenick, another group of quaternary ammonium functional silicones is disclosed along with a two step method for making them. This method involves reacting a silicone polyether having a terminal xe2x80x94OH group with epichlorohydrin (an epoxide), and the resulting product is reacted with a tertiary amine.
A group of quaternary ammonium functional silanes covalently bonded to glass is disclosed by Tally et al. in U.S. Pat. No. 4,118,316. These materials are made by reacting amino silanes and glass beads to form silanized glass, followed by treatment with a halohydrin.
Considering the large number of applications possible, such as in personal care and textiles, there is a need for new quaternary ammonium functional silicones and silanes and methods for making them. The present invention is directed to filling these needs.
It is an object of this invention to provide novel, silicon based quaternary ammonium functional compositions. Thus, the invention relates to a silicon based quaternary ammonium functional composition comprising the group:
xe2x80x94R1xe2x80x94Zxe2x80x94Q3
where, xe2x80x94R1xe2x80x94 is either a divalent hydrocarbon group, which may optionally incorporate ether or ester functionality, or xe2x80x94R17N(Q1)R18xe2x80x94, and is covalently bonded to Si in an unsupported silicone or silane;
xe2x80x94Zxe2x80x94 is xe2x80x94C(O)Oxe2x80x94 or xe2x80x94N(Q2)xe2x80x94;
xe2x80x94Q3 is xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
xe2x80x94R17xe2x80x94 and xe2x80x94R18xe2x80x94 are independently divalent hydrocarbon groups that may optionally incorporate ether or ester functionality;
xe2x80x94Q1 and Q2 are independently xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
Y is a divalent hydrocarbon group;
R3 is a monovalent hydrocarbon group or hydrogen;
R4, R5 and R6 are independently monovalent hydrocarbon groups; and
Xxe2x88x92 is a counter ion,
with the proviso that at least one of xe2x80x94Q1, xe2x80x94Q2 and xe2x80x94Q3 is xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92.
It is a further object of this invention to provide methods to make silicon based quaternary ammonium functional compositions. Thus, this invention further relates to a method of making a silicon based quaternary ammonium functional composition, the method comprising:
reacting
(1) a quaternary ammonium compound having a substituent group, the substituent group having epoxide or halohydrin functionality, with
(2) a silicon based material having an organofunctional group, the silicon based material being an unsupported silicone or silane and the organofunctional group having carboxy or amino functionality.
The compositions according to the present invention are silicon based quaternary ammonium functional compositions, including those that comprise the group:
xe2x80x94R1xe2x80x94Zxe2x80x94Q3
where, xe2x80x94R1xe2x80x94 is either a divalent hydrocarbon group, which may optionally incorporate ether or ester functionality, or xe2x80x94R17N(Q1)R18xe2x80x94, and is covalently bonded to Si in an unsupported silicone or silane;
xe2x80x94Zxe2x80x94 is xe2x80x94C(O)Oxe2x80x94 or xe2x80x94N(Q2)xe2x80x94;
xe2x80x94Q3 is xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
xe2x80x94R17xe2x80x94 and xe2x80x94R18xe2x80x94 are independently divalent hydrocarbon groups that may optionally incorporate ether or ester functionality;
xe2x80x94Q1 and Q2 are independently xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
Y is a divalent hydrocarbon group;
R3 is a monovalent hydrocarbon group or hydrogen;
R4, R5 and R6 are independently monovalent hydrocarbon groups; and
Xxe2x88x92 is a counter ion,
with the proviso that at least one of xe2x80x94Q1, xe2x80x94Q2 and xe2x80x94Q3 is xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92.
It should be understood that in this disclosure and the claims that follow that particular xe2x80x9cRxe2x80x9d and similarly designated groups may exhibit some variation, unless specifically stated otherwise. That is, variation allowed by the overall definition given. For example, if it is stated that R99 in a certain chemical structure can be hydrogen, chlorine or a monovalent hydrocarbon, then the R99""s in a particular sample of the corresponding material may actually vary among the stated possibilities of hydrogen, chlorine or various monovalent hydrocarbons (and still be covered by a corresponding claim). This variation can be between or within molecules as applicable.
As to optional xe2x80x9cincorporatedxe2x80x9d functional groups, it should be understood that these may be xe2x80x9cinternalxe2x80x9d as well as pendant groups. Such groups would not be included in any tally given for number of carbons, unless otherwise indicated.
It should be understood that in this specification and the claims that follow that xe2x80x9cunsupportedxe2x80x9d silicones and silanes are free silicone and silanes. That is, silicones and silanes that are not covalently bonded to supports such as glass beads. Furthermore, all references to silicones and silanes in this disclosure and the claims that follow should be taken to be to unsupported silicones and silanes, unless indicated otherwise. Examples of supported materials can be found in Talley et al. (U.S. Pat. No. 4,118,316), which is hereby incorporated by reference for same.
For the compositions of the present invention, generally acceptable counter ions include halogen ions, such as chlorine and bromine, as well as others such as acetate and methyl sulfate. Counter ions are preferably non-reactive internally; that is, non-reactive with the corresponding silicone or silane portion of the overall molecule or others like it.
The compositions of the present invention, notably the silicones, have application in personal care including hair, skin and nail conditioning and treatment. They may also be used as antimicrobials, notably the silanes. Some uses of the compositions of the present invention are considered in detail in a companion application to this one, filed the same day and entitled, xe2x80x9cSilicon Based Quaternary Ammonium Functional Compositions and Their Applicationsxe2x80x9d, which is hereby incorporated by reference.
One preferred embodiment of the compositions of the present invention has the groups xe2x80x94Q1, xe2x80x94Q2 and/or xe2x80x94Q3 (as defined previously or those corresponding) as xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92. R4, R5, R6 and Xxe2x88x92 are as defined previously especially where R4, R5 and R6 are independently monovalent hydrocarbon groups having up to 20 carbons, preferably methyl, dodecyl or octadecyl.
It should be understood that in the context of this disclosure and the claims that follow that ranges disclosed should be taken to specifically disclose not only the endpoint(s) of the range, but all the values subsumed in the range individually. For example, a stated range of 1 to 10 discloses not only 1 and 10, but also 2, 2.7, 5.5 and all other values in the range. Similarly, a range of C1-C5 hydrocarbons would disclose C2, C3 and C4 hydrocarbons, as well as C1 and C5 hydrocarbons.
Another preferred embodiment of the compositions of the present invention is a silicone comprising the group xe2x80x94R1xe2x80x94Zxe2x80x94Q3 where such group may be expressed as:
xe2x80x94R17N(Q1)R18xe2x80x94N(Q2)xe2x80x94Q3
where, xe2x80x94R17xe2x80x94 is a divalent hydrocarbon group, which may optionally incorporate ether or ester functionality, and is covalently bonded to Si in an unsupported silicone;
xe2x80x94R18xe2x80x94 is a divalent hydrocarbon group that may optionally incorporate ether or ester functionality;
at least one of Q1, Q2 and Q3 is of the formula
xe2x80x94CH(R3)CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92 with all of Q1, Q2 and Q3 remaining being independently hydrogen or a monovalent hydrocarbon group which may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
Y is a divalent hydrocarbon group;
R3 is a monovalent hydrocarbon group or hydrogen;
R4, R5 and R6 are independently monovalent hydrocarbon groups, especially those having up to 20 carbons, preferably methyl, dodecyl or octadecyl; and
Xxe2x88x92 is a counter ion.
As to the immediately aforementioned embodiment, as well as to the compositions of the present invention generally (where groups corresponding are present), it is frequently preferred that R17 is CH2CH(CH3)CH2 or (CH2)3 and that independently R18 is CH2CH2. Correspondingly and independently, it is often preferred that at least one of Q1, Q2 and Q3 is of the formula CH2CH(OH)CH2N+(CH3)2(R6)Xxe2x88x92, where R6 is a monovalent hydrocarbon group, especially one having up to 20 carbons, preferably methyl, dodecyl or octadecyl, and Xxe2x88x92 is a counter ion. Where any of Q1, Q2 and Q3 are monovalent hydrocarbon groups, one preference is methyl.
An embodiment of the compositions of the present invention of special interest (referred to herein as xe2x80x9cthe type I embodimentxe2x80x9d) is a silicone of average formula (to be taken here and in the claims that follow as based on the silicones molecules and their number present in a given sample): 
where R21, R22, R23, R30 and R31 are independently hydroxy or phenoxy, or alkoxy or monovalent hydrocarbon groups (especially, in the latter two instances, those having carbons or less, preferably 1 or 2 carbons);
R24, R25 and R27 are independently monovalent hydrocarbon groups, especially those having 20 carbons or less;
R28 is a monovalent hydrocarbon group, especially having 20 carbons or less, or contains nitrogen and may at least in part represent a group or groups of the form xe2x80x94R1xe2x80x94Zxe2x80x94Q3;
R26 and R29 contain nitrogen and where present represent, at least in part, a group or groups of the form xe2x80x94R1xe2x80x94Zxe2x80x94Q3;
xe2x80x94R1xe2x80x94 is either a divalent hydrocarbon group, that may optionally incorporate ether or ester functionality, or xe2x80x94R17N(Q1)R18xe2x80x94, especially xe2x80x94CH2CH(CH3)CH2xe2x80x94N(Q1)xe2x80x94CH2CH2xe2x80x94 or xe2x80x94(CH2)3xe2x80x94N(Q1)xe2x80x94CH2CH2xe2x80x94 for the latter;
xe2x80x94R17xe2x80x94 and xe2x80x94R18xe2x80x94 are independently divalent hydrocarbon groups that may optionally incorporate ether or ester functionality;
xe2x80x94Q1 is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
R4, R5 and R6 are independently monovalent hydrocarbon groups;
Xxe2x88x92 is a counter ion;
xe2x80x94Zxe2x80x94 is xe2x80x94N(Q2)xe2x80x94;
xe2x80x94Q3 andxe2x80x94Q2 are independently xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
a, b, d, e and g are greater than or equal to 0;
a=0 to 2+g;
b=0 to 2+g;
d=0 to 500, especially 0 to 400;
e=0 to 100, especially 0 to 50;
g=0 to 100, especially 0 to 5;
a+b is greater than or equal to 2; and
e+b greater than 0,
with the proviso that at least a portion of Q1, Q2, and Q3 present in the composition, especially where at least 10 percent (preferably 15 to 75 percent and more preferably 20 to 60 percent), with the percentage based on the total number of these groups present in the composition, is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92.
The positions of the R and similarly designated groups shown in the formula in the last mentioned embodiment, as well as all others disclosed or claimed herein, should not be taken as indicating any stereospecificity. Furthermore, it should be understood that the immediately preceding formula is not totally structural; for example, if d was equal to 3 therein, then the composition would have 3 of the subunits corresponding to the d subscript somewhere between each molecule""s end groups on average, but not necessarily contiguously.
In the last mentioned embodiment, it is usually preferred that at least 10 percent (more preferably 15 to 75 percent and most preferably 20 to 60 percent) of the total of Q1, Q2 and Q3 (the percentage based on the total number of these groups in the composition) is of the formula CH2CH(OH)CH2N+(CH3)2(R6)Xxe2x88x92, where R6 is a monovalent hydrocarbon, especially one having up to 20 carbons, preferably methyl, dodecyl or octadecyl, and Xxe2x88x92 is a counter ion. It is often preferred that all remaining Q1, Q2 and Q3 are independently hydrogen or methyl. Additionally, it is usually preferred that (e+b)/(a+b+d+e+g) is greater than or equal to 0.005, more preferably 0.01 to 0.04 and most preferably 0.015 to 0.03.
An embodiment of the compositions of the present invention of great interest (herein xe2x80x9cthe type II embodimentxe2x80x9d) is defined as the type I embodiment with the following more specific selections for the groups indicated:
R21, R22, R23, R30 and R31 are independently hydroxy, or alkoxy or monovalent hydrocarbon groups having 1 to 20 carbons;
R24, R25 and R27 are independently monovalent hydrocarbon groups having 1 to 20 carbons;
R28 is a monovalent hydrocarbon group having 1 to 20 carbons, or contains nitrogen and may at least in part represent a group or groups of the form xe2x80x94R1xe2x80x94Zxe2x80x94Q3;
xe2x80x94R1xe2x80x94 is either a divalent hydrocarbon group having 1 to 20 carbons, that may optionally incorporate ether or ester functionality, or xe2x80x94R17N(Q1)R18xe2x80x94;
xe2x80x94R17xe2x80x94 and xe2x80x94R18xe2x80x94 are independently divalent hydrocarbon groups having 1 to 20 carbons that may optionally incorporate ether or ester functionality;
xe2x80x94Q1 is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group having 1 to 20 carbons that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
R4, R5 and R 6 are independently monovalent hydrocarbon groups having 1 to 20 carbons;
Xxe2x88x92 is a counter ion;
xe2x80x94Q3 and xe2x80x94Q2 are independently xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group having 1 to 20 carbons that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
d=0 to 400;
e=0 to 50;
g=0 to 50; and
(e+b)/(a+b+d+e+g)=0.005 to 0.05;
with the proviso that 10 to 75 percent of Q1, Q2, and Q3 present in the composition is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92.
Another embodiment of the compositions of the present invention of great interest (herein xe2x80x9cthe type III embodimentxe2x80x9d) is defined as the type I embodiment with the following more specific selections for the groups indicated:
R21, R22, R23, R30 and R31 are independently hydroxy, methoxy or methyl groups;
R24, R25 and R27 are methyl groups;
R28 is a methyl group, or contains nitrogen and may at least in part represent a group or groups of the form xe2x80x94R1xe2x80x94Zxe2x80x94Q3;
xe2x80x94R1xe2x80x94 is either a propylene group or xe2x80x94R17N(Q1)R18xe2x80x94;
xe2x80x94R17xe2x80x94 is a propylene or an isobutylene group and xe2x80x94R18xe2x80x94 is an ethylene group;
xe2x80x94Q1 is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a methyl group;
R4 and R5 are methyl groups;
R6 is a methyl, dodecyl or octadecyl group;
Xxe2x88x92 is a counter ion;
xe2x80x94Q3 and xe2x80x94Q2 are independently xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R5)Xxe2x88x92, hydrogen or a methyl group;
d=50 to 150;
e=0 to 10;
g=0 to 5; and
(e+b)/(a+b+d+e+g)=0.01 to 0.03,
with the proviso that 25 to 40 percent of Q1, Q2, and Q3 present in the composition is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92.
A further embodiment of the compositions of the present invention of special interest is a silane of the formula: 
wherein, xe2x80x94R11 is a monovalent hydrocarbon group or xe2x80x94OR41, where xe2x80x94R41 is hydrogen or a monovalent hydrocarbon group;
xe2x80x94R12 is a monovalent hydrocarbon group or xe2x80x94OR42, where xe2x80x94R42 is hydrogen or a monovalent hydrocarbon group;
xe2x80x94R13 is a monovalent hydrocarbon group or xe2x80x94OR43, where xe2x80x94R43 is hydrogen or a monovalent hydrocarbon group;
xe2x80x94R1xe2x80x94 is either a divalent hydrocarbon group that may optionally incorporate ether or ester functionality, or xe2x80x94R17N(Q1)R18xe2x80x94;
xe2x80x94R17xe2x80x94 and xe2x80x94R18xe2x80x94 are independently divalent hydrocarbon groups that may optionally incorporate ether or ester functionality;
xe2x80x94Q1 is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality;
R4, R5 and R6 are independently monovalent hydrocarbon groups; and
Xxe2x88x92 is a counter ion.
xe2x80x94Zxe2x80x94 is xe2x80x94N(Q2)xe2x80x94; and
xe2x80x94Q3 and xe2x80x94Q2 are independently xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92, hydrogen or a monovalent hydrocarbon group that may optionally incorporate hydroxy, diol, amide, ether or ester functionality,
with the proviso that at least one of xe2x80x94Q1, xe2x80x94Q2 and xe2x80x94Q3 is xe2x80x94CH2CH(OH)CH2N+(R4)(R5)(R6)Xxe2x88x92.
In the silanes of the present invention, where an R group is a hydrocarbon, it is preferably one having 20 carbons or less, and in the case of R4, R5 and R6, especially and independently methyl, dodecyl or octadecyl. One preferred group of silanes has R11, R12, and R13 as xe2x80x94OCH3 and R1 as xe2x80x94(CH2)3xe2x80x94.
The methods of the present invention are directed to making silicon based quaternary ammonium functional compositions. In general, these methods comprise reacting:
(1) a quaternary ammonium compound having a substituent group, the substituent group having epoxide or halohydrin functionality, with
(2) a silicon based material having an organofunctional group, the silicon based material being an unsupported silicone or silane and the organofunctional group having carboxy or amino functionality.
Reaction takes place between the aforementioned functionalities of the substituent and organofunctional groups.
Reaction may be made to take place by simply putting the reactants in contact, which should be taken as the implied minimum requirement to obtain reaction (performing the xe2x80x9creactingxe2x80x9d step) under the circumstances. However, it is usually preferred to mix the reactants and/or heat them, especially to reflux of an added solvent, such as an alcohol like isopropanol. Appropriate catalysts may be employed. It may be advantageous to use an excess of silicone or silane reactant as the presence of residual epoxy or halohydrin reactants in products is usually undesirable (especially the epoxide); such undesirable residual materials would have to be further reacted or removed in an extra step.
It has been found generally that tertiary amines do not add readily to epoxides. This situation can be improved if the reaction mixture is acidified (especially stoichiometrically) or the tertiary amine is pretreated with -acid (converted to its acid salt).
Throughout this disclosure and the claims that follow, it should be understood that xe2x80x9caminoxe2x80x9d may refer to (at least) primary, secondary and/or tertiary amines. In addition, unless otherwise indicated, reference to an organic acid or base includes one to its ionized form (as well as its salts) and vice versa. For example, reference to a carboxylic acid would include one to the corresponding carboxylate.
One preferred group of epoxy functional quaternary ammonium compounds for use in the application of the methods of the present invention is represented by the formula:
xe2x80x83CH2(O)CHYN+(R4)(R5)(R6)Xxe2x88x92
where, Y is a divalent hydrocarbon group, especially methylene;
R4, R5 and R6 are independently monovalent hydrocarbon groups, especially those having up to 20 carbons and preferably methyl, dodecyl or octadecyl; and
Xxe2x88x92 is a counter ion, especially chloride or bromide.
Specific examples from this group are glycidyl trimethyl ammonium chloride and the corresponding bromide. Non-terminal epoxides may also be used, but terminal epoxides (such as those of the group described here) are generally preferred.
A preferred group of halohydrin functional quaternary ammonium compounds for use in the application of the methods of the present invention is represented by:
(X1)CH2CH(OH)YN+(R4)(R5)(R6)Xxe2x88x92
where X1 is a halogen, especially chlorine or bromine;
Y is a divalent hydrocarbon group, especially methylene;
R4, R5 and R6 are independently monovalent hydrocarbon groups, especially those having up to 20 carbons and preferably methyl, dodecyl or octadecyl; and
Xxe2x88x92 is a counter ion, especially chloride or bromide.
Specific examples from this group are 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyldodecyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyloctadecyl ammonium chloride and the corresponding bromides. (Some combination of these specific halohydrins, other members of the group described here and/or members of the previously recited group of epoxides may also be employed.) Non-terminal halohydrins may also be used, but terminal halohydrins (such as those of the group here) are generally preferred.
Some more specific silicones which are often useful as reactants in the methods of the present invention include those of number average molecular weight 1000 to 100,000 (especially 5000 to 50,000), especially polydimethylsiloxanes that are preferably trimethyl end blocked, and where amino functional, those containing 0.1 to 2.0 milliequivalents amino functionality per gram of silicone (on average based on the amino nitrogen of primary and secondary amino groups in all silicones present in the given sample) being preferred. Examples of amino groups that may be present in these silicones include aminopropyl, aminoethyl aminopropyl or aminoethyl aminoisobutyl.
Often useful as reactants in the methods of the present invention are silanes of the following structure: 
where, R11, R12 and R13 are independently methoxy or ethoxy groups, and R14 is an aminopropyl, an aminoethyl aminopropyl or an aminoethyl aminoisobutyl group.
It is of note that the non-silanol silanes of the present invention can be prepared in relatively pure form where synthesis is conducted under anhydrous conditions. Generally, however, it is easier to prepare these silanes in aqueous alcohols. In the latter case, the product will ordinarily be a solution of partially hydrolyzed silanes and silane oligomers; this may be preferred, as silanes used as primers to promote adhesion of organic polymers to mineral surfaces are often applied from aqueous alcohol solutions.
Molecular weight of the products of the methods of the present invention can be controlled by selection of reactants, usually most practically the silicone or silane reactant, as well by selection of the ratio of reactants. Quaternary ammonium content can be controlled through reaction/reactant stoichiometry; that is, by the ratio of reactants. Molecular weight and quaternary ammonium content can be closely correlated to many properties of these materials.
It has been noted that properties of the compositions of the present invention are in large part predictable from their molecular weight in combination with their quaternary ammonium content. The viscosity of these materials (and hence their processing difficulty in most cases) increases fairly regularly with molecular weight, and dramatically at a given molecular weight as the quaternary ammonium content increases. As to water solubility, higher molecular weight materials are generally water insoluble, unless the quaternary ammonium content is very high, but lower molecular weight materials are generally water soluble at much lower (reasonable) quaternary ammonium content.
In one embodiment of the methods of the present invention (specifically of the general class previously recited), the silicone reactant contains on average (taken here and in the claims that follow as based on the total number of silicone reactant molecules used) 0.01 to 8.1, preferably 0.1 to 2.0, more preferably 0.2 to 0.9 and most preferably 0.4 to 0.75 milliequivalents of amine nitrogen per gram, considering only primary and secondary amines. The quaternary ammonium reactant is selected from the group consisting of glycidyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyldodecyl ammonium chloride, 3-chloro-2-hydroxypropyl dimethyloctadecyl ammonium chloride, the corresponding bromide of any of these and some combination of any of these chlorides and bromides. The average molar ratio during reaction of quaternary ammonium reactant to total amine hydrogen in the silicone reactant, considering only primary and secondary amines, is at least 1:10, preferably 1:6 to 9:10. This last ratio, for most practical purposes, has an upper limit of 1:1, since excess quaternary ammonium reactant would have to be removed or further reacted in a later step as its presence in products is usually quite objectionable (especially an epoxide)
The methods of the present invention include those for modifying certain compositions of the present invention to form more complex compositions of the present invention (derivatives). In one particular case, diol or amide functionality is added, the method comprising reacting:
(1) a composition according to the present invention which comprises the group xe2x80x94R1xe2x80x94Zxe2x80x94Q3 as defined previously, wherein at least a portion of R1 is a secondary amine or at least a portion of Z is a primary or secondary amine, with
(2) a material, T, where T has organofunctionality selected from the group consisting of lactone, carboxy and epoxy. Specific examples of T include glycidol and gamma butyrolactone.
Reaction may be made to take place by simply putting the reactants in contact, which should be taken as the implied minimum requirement to obtain reaction (perform the xe2x80x9creactingxe2x80x9d step) under the circumstances. However, it is usually preferred to mix the reactants and/or heat them, especially to reflux of an added solvent, such as an alcohol like isopropanol. Appropriate catalysts may be employed.
It may be advantageous to use an excess of silicone or silane reactant as the presence of residual halohydrin or epoxide containing reactants in the products is usually undesirable (especially the epoxide) and would have to be removed or further reacted in a later step.
It may be convenient to describe compositions in terms of a method that can be used to make them. This is often termed the xe2x80x9cproduct by processxe2x80x9d definition of a composition. The compositions of the present invention should be taken to include products of the methods described herein.